CN102757037B - Method for preparing graphite oxide - Google Patents
Method for preparing graphite oxide Download PDFInfo
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- CN102757037B CN102757037B CN201110105736.1A CN201110105736A CN102757037B CN 102757037 B CN102757037 B CN 102757037B CN 201110105736 A CN201110105736 A CN 201110105736A CN 102757037 B CN102757037 B CN 102757037B
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Abstract
The invention discloses to the field of graphite oxide material and discloses a preparation method of graphite oxide. The preparation method comprises the following steps of: cooling concentrated sulphuric acid to 0 DEG C with ice bath; sequentially adding graphite and KMnO4 into the concentrated sulphuric acid, and reacting; heating a reaction system to 35 minus or plus 3 DEG C and continuing to react; slowly adding the reaction system into water, and controlling temperature of the reaction system to be lower than 100 DEG C, thus preparing the graphite oxide. According to the preparation method of graphite oxide disclosed by the invention, the traditional high temperature hydrolysis manner is changed, the reaction system is added into the water, and the reaction temperature is controlled to be lower than 100 DEG C, thus intense exothermic situation in a reaction process is reduced; meanwhile, viscosity of the reaction system is greatly reduced in the preparation method, and expansion of graphite, caused by overhigh local temperature, can be avoided.
Description
Technical field
The present invention relates to graphite oxide field, relate in particular to a kind of preparation method of graphite oxide.
Background technology
Since the strong K sea nurse of the peace moral of Univ Manchester UK (Andre K.Geim) etc. was prepared grapheme material in 2004, because being subject to people, its unique structure and photoelectric property pay close attention to widely.Graphene is called " nova " that is rising in Materials science and Condensed Matter Physics field, many novelties that it has and unique character and potential application are just attracting many scientific workers.Single-layer graphene has large specific surface area, good conduction, heat conductivility and low thermal expansivity.As: 1. high strength, Young molar weight, (1,100GPa), breaking tenacity: (125GPa); 2. high heat conductance, (5,000W/mK); 3. high conductivity, carrier transport rate, (200,000cm
2/ V*s); 4. high specific surface area, (calculated value: 2,630m
2/ g).Especially its high conductivity matter, the textural property of large specific surface character and the nanoscale of its unimolecular layer two dimension can be used as electrode materials in ultracapacitor and lithium ion battery.The preparation method of Graphene mainly comprises at present: micromechanics stripping method, ultrahigh vacuum(HHV) Graphene epitaxial growth method, oxidation reduction process, chemical Vapor deposition process (CVD), solvent stripping method etc.
But in these methods, oxidation reduction process is at present unique a kind of preparation method who has cheap and extensive preparation advantage concurrently.Preparing by oxidation reduction process in the process of Graphene, a large amount of preparations of graphite oxide are again bottlenecks.Because add a large amount of water in the pyrohydrolysis stage of graphite oxidation (graphite and vitriol oil etc.) in reaction system, while preparation on a large scale system heat release violent, temperature rise is comparatively fast larger test to equipment.In addition, because system viscosity is large, if stir the too high graphite expansion that easily causes of uneven local temperature, prepare unsuccessfully.
Summary of the invention
The object of the present invention is to provide a kind of temperature of reaction can be controlled at the preparation method of the graphite oxide at 100 DEG C.
Technical scheme of the present invention is as follows:
S1, use the ice bath type of cooling, 230～460mL vitriol oil is cooled to 0 DEG C;
S2, purity 99.5% graphite is joined in the vitriol oil, then slowly add potassium permanganate (KMnO
4), and control 0～20 DEG C of temperature of reaction (preferably 10 DEG C), the 2～4h of insulated and stirred reaction subsequently (preferably 3h); Wherein, graphite and KMnO
4mass ratio be 1: 3; Wherein, select graphite and KMnO
4respectively 20g and 60g of quality;
S3, the reaction system of step S2 is warming up to 35 ± 3 DEG C, i.e. insulated and stirred reaction 0.5～1h at 32～38 DEG C;
S4, the reaction system of step S3 is slowly poured into 460～920mL temperature is in the water of 20～80 DEG C, and controls temperature of reaction system and be less than 100 DEG C, and insulated and stirred reaction 15～45min; Then, adding concentration is the hydrogen peroxide (H of 30wt%
2o
2) do not produce gas to reaction system till; Filtered while hot obtains solid product subsequently, and the salt acid elution solid product that is 10wt% by a large amount of concentration does not contain SO to filtrate
4 2～till; Finally, dried solid product 24～48h in washing, suction filtration, 50 DEG C of vacuum drying ovens, obtains graphite oxide.
The preparation method of graphite oxide provided by the invention, by changing the mode of conventional high-temperature hydrolysis, water is slowly joined in reaction system, reaction system is added in water, and control temperature of reaction and be less than 100 DEG C, thereby reduce the very exothermic situation in reaction process; Meanwhile, this preparation method also greatly reduces reaction system viscosity, and can avoid causing because local temperature is too high graphite expansion.
Brief description of the drawings
Fig. 1 is graphite oxide preparation method's of the present invention process flow sheet;
Fig. 2 is the XRD phenogram of this natural flake graphite;
Fig. 3 is the XRD phenogram of the graphite oxide that makes of the inventive method.
Embodiment
Graphite oxide preparation method provided by the invention, as shown in Figure 1, its technique preparation process is as follows:
S1, use the ice bath type of cooling, 203～460mL vitriol oil is cooled to 0 DEG C;
S2, purity 99.5% graphite is joined in the vitriol oil, then slowly add potassium permanganate (KMnO
4), and control 0～20 DEG C of temperature of reaction (preferably 10 DEG C), the 2～4h of insulated and stirred reaction subsequently (preferably 3h); Wherein, graphite and KMnO
4mass ratio be 1: 3; Wherein, select graphite and KMnO
4respectively 20g and 60g of quality;
S3, the reaction system of step S2 is warming up to 35 ± 3 DEG C, i.e. insulated and stirred reaction 0.5～1h at 32～38 DEG C;
S4, the reaction system of step S3 is slowly poured into 460～920mL temperature is in the water of 20～80 DEG C, and control temperature of reaction system be less than 100 DEG C (as, 10 DEG C, 20 DEG C, 40 DEG C, 60 DEG C, 70 DEG C, 90 DEG C etc.), and insulated and stirred reaction 15～45min; Then, adding concentration is the hydrogen peroxide (H of 30wt%
2o
2) do not produce gas to reaction system till; Filtered while hot obtains solid product subsequently, and the salt acid elution solid product that is 10wt% by a large amount of concentration does not contain SO to filtrate
4 2～till; Finally, dried solid product 24～48h in washing, suction filtration, 50 DEG C of vacuum drying ovens, obtains graphite oxide.
Fig. 2 is the XRD phenogram of natural flake graphite in the present invention; As can be seen from Figure 2, natural flake graphite is that graphite (002) diffraction peak appears in 26 ° of left and right at 2 θ angles.
Fig. 3 is the XRD phenogram of the graphite oxide that makes of the inventive method; From Fig. 3, in graphite oxide XRD figure, can find out, after graphite oxidation, diffraction peak moves to 12 ° of left and right, and sample layer spacing increases, and graphite (002) peak position place is substantially without diffraction peak, illustrates that graphite is substantially all oxidized, retains without graphite-structure.Thereby proof has obtained the graphite oxide that we want.
In a word, the preparation method of graphite oxide provided by the invention, by changing the mode of conventional high-temperature hydrolysis, water is slowly joined in reaction system, reaction system is added in water, and control temperature of reaction and be less than 100 DEG C, thereby reduce the very exothermic situation in reaction process; Meanwhile, this preparation method also greatly reduces reaction system viscosity, and can avoid causing because local temperature is too high graphite expansion.
Below preferred embodiment of the present invention is described in further detail.
Embodiment 1
S1, use the ice bath type of cooling, the 460mL vitriol oil is cooled to 0 DEG C;
S2, the 20g graphite of purity 99.5% is joined in the vitriol oil, then slowly add the KMnO of 60g
4, and control 0 DEG C of temperature of reaction, the 4h of insulated and stirred reaction subsequently;
S3, the reaction system of step S2 is warming up to 38 DEG C, insulated and stirred reaction 1h;
S4, the reaction system of step S3 is slowly poured into 460mL temperature is in the water of 20 DEG C, and temperature of reaction system is controlled to 20 DEG C, and insulated and stirred reaction 15min; Then, adding concentration is the hydrogen peroxide (H of 30wt%
2o
2) do not produce gas to reaction system till; Filtered while hot obtains solid product subsequently, and the salt acid elution solid product that is 10wt% by a large amount of concentration does not contain SO to filtrate
4 2-till; Finally, dried solid product 48h in washing, suction filtration, 50 DEG C of vacuum drying ovens, obtains graphite oxide.
Embodiment 2
S1, use the ice bath type of cooling, the 230mL vitriol oil is cooled to 0 DEG C;
S2, the 20g graphite of purity 99.5% is joined in the vitriol oil, then slowly add the KMnO of 60g
4, and control 20 DEG C of temperature of reaction, the 2h of insulated and stirred reaction subsequently;
S3, the reaction system of step S2 is warming up to 35 DEG C of insulated and stirred reaction 0.5h;
S4, the reaction system of step S3 is slowly poured into 700mL temperature is in the water of 80 DEG C, while temperature of reaction system is controlled to 60 DEG C, and insulated and stirred reaction 30min; Then, adding concentration is the hydrogen peroxide (H of 30wt%
2o
2) do not produce gas to reaction system till; Filtered while hot obtains solid product subsequently, and the salt acid elution solid product that is 10wt% by a large amount of concentration does not contain SO to filtrate
4 2-till; Finally, dried solid product 36h in washing, suction filtration, 50 DEG C of vacuum drying ovens, obtains graphite oxide.
Embodiment 3
S1, use the ice bath type of cooling, the 350mL vitriol oil is cooled to 0 DEG C;
S2, the 20g graphite of purity 99.5% is joined in the vitriol oil, then slowly add the KMnO of 60g
4, and control 10 DEG C of temperature of reaction, the 3h of insulated and stirred reaction subsequently;
S3, the reaction system of step S2 is warming up to 32 DEG C of insulated and stirred reaction 0.8h;
S4, the reaction system of step S3 is slowly poured into 920mL temperature is in the water of 50 DEG C, while temperature of reaction system is controlled to 90 DEG C, and insulated and stirred reaction 45min; Then, adding concentration is the hydrogen peroxide (H of 30wt%
2o
2) do not produce gas to reaction system till; Filtered while hot obtains solid product subsequently, and the salt acid elution solid product that is 10wt% by a large amount of concentration does not contain SO to filtrate
4 2-till; Finally, dried solid product 24h in washing, suction filtration, 50 DEG C of vacuum drying ovens, obtains graphite oxide.
Should be understood that, the above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.
Claims (8)
1. a preparation method for graphite oxide, is characterized in that, this preparation method comprises the steps:
S1, the vitriol oil is cooled to 0 DEG C;
S2, in the vitriol oil in step S1, add dry graphite, then add potassium permanganate, and at 0～20 DEG C insulated and stirred reaction 2～4h;
S3, the reaction system in step S2 is warming up at 32～38 DEG C to insulated and stirred reaction 0.5～1h;
S4, the reaction system of step S3 is slowly poured into 460～920mL temperature is in the water of 20～80 DEG C, and controlling temperature of reaction system is 10 DEG C, 20 DEG C, 40 DEG C, 60 DEG C, 70 DEG C or 90 DEG C, and insulated and stirred reaction 15～45min, subsequently toward adding hydrogen peroxide, and after purifying treatment, obtain described graphite oxide;
Wherein, in step S4, described purifying treatment also comprises the steps:
S41, filter reaction system, use subsequently salt acid elution in filtrate not till containing sulfate radicals, obtain solid product;
S42, washing, suction filtration the solid product obtaining in vacuum drying step S41 at 50 DEG C, cooling after, obtain described graphite oxide.
2. preparation method according to claim 1, is characterized in that, in described step S1, adopts the ice bath type of cooling that the vitriol oil is cooled to 0 DEG C.
3. preparation method according to claim 2, is characterized in that, the volume number of the described vitriol oil is 230～460ml.
4. preparation method according to claim 1, is characterized in that, in described step S2, the mass ratio of graphite and potassium permanganate is 1:3.
5. preparation method according to claim 4, is characterized in that, temperature of reaction is 10 DEG C.
6. preparation method according to claim 5, is characterized in that, the reaction times is 3h.
7. preparation method according to claim 1, is characterized in that, the concentration of described hydrogen peroxide is 30wt%.
8. preparation method according to claim 1, is characterized in that, the concentration of described hydrochloric acid is 10wt%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110105736.1A CN102757037B (en) | 2011-04-26 | 2011-04-26 | Method for preparing graphite oxide |
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|---|---|---|---|
| CN201110105736.1A CN102757037B (en) | 2011-04-26 | 2011-04-26 | Method for preparing graphite oxide |
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| CN102757037A CN102757037A (en) | 2012-10-31 |
| CN102757037B true CN102757037B (en) | 2014-11-05 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104071772B (en) * | 2013-03-25 | 2017-07-18 | 绿琪（北京）生物科技有限公司 | A kind of equipment of preparation of industrialization graphite oxide |
| CN105621403A (en) * | 2016-02-01 | 2016-06-01 | 江南石墨烯研究院 | Efficient and environment-friendly method for preparing graphite oxide |
| CN109970054A (en) * | 2019-04-30 | 2019-07-05 | 重庆大学 | Prepare graphite oxide method and its graphite oxide obtained |
| CN109970053A (en) * | 2019-04-30 | 2019-07-05 | 重庆大学 | Prepare graphite oxide method and its graphite oxide obtained |
| CN110482540B (en) * | 2019-09-27 | 2022-11-08 | 徐州汇墨新材料科技有限公司 | Preparation method of graphene oxide powder with good dispersibility |
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2011
- 2011-04-26 CN CN201110105736.1A patent/CN102757037B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| Daniela C. Marcano et al..Improved synthesis of graphene oxide.《American Chemical Society》.2010,第4卷(第8期), * |
| Improved synthesis of graphene oxide;Daniela C. Marcano et al.;《American Chemical Society》;20101231;第4卷(第8期);4806-4814 * |
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